ASYMMETRIC SYNTHESIS OF 1,3-POLYOLS VIA HYDROSILATION

提出的研究探索了一种新的方法，用于合成1,3-二醇和1,3,5-三醇官能团通过分子内氢化异构醇。烯烃的表面选择性是通过使用手性助剂（aC2对称联萘酚）连接到起始材料的硅原子来实现的。本文提出，手性助剂将能够在随后的转化中进一步利用在整个产物中传递立体化学信息。因此，通过进一步的功能化和操作，应该产生1,3-多元醇功能化。由此提出手性助剂在从产物中分离和回收前可以控制三个中心的绝对立体化学。1,3-多元醇的重要性在天然产品世界中广泛存在。一些抗生素、抗肿瘤和免疫抑制化合物含有这种功能。其中一种这样的化合物（-）discodermolide含有三个1,3,5-三醇单元，其中一个应该可以用所提出的方法获得。为了进一步探索硅系链方法的范围，建议使用氢化方法的变体来制作所有三个构建块，并且使用硅系链烯烃环闭合复分解协议来制作天然产物的主干的重要连接。

The proposed research explores a novel methodology for the synthesis of 1,3-diol and 1,3,5-triol functionalities via the intramolecular hydrosilation of homoallylic alcohols. Alkene facial selectivity is afforded by the use of a chiral auxiliary (aC2 symmetric binaphthol) attached to the silicon atom of the starting material. It is proposed that the chiral auxiliary will then be able to be further utilized in relaying stereochemical information throughout the product in subsequent transformations. Thus through further functionalization and manipulation 1,3-polyol functionalities should be produced. In such a way, it is proposed that the chiral auxiliary can control the absolute stereochemistry of three centers before being cleaved from the product and recycled. The importance of 1,3-polyols is born out in their vast presence in the natural product world. Several antibiotic, anti-tumor and immunosuppressant compounds contain this functionality. One such compound, (-) discodermolide, contains three 1,3,5-triol units, one of which should be accessible using the proposed methodology. To further explore the scope of silicon tethered methodology, it is proposed that all three building blocks be made using variations of the hydrosilation methodology, and an important connection in making the backbone of the natural product be performed using a silicon tethered alkene ring closing metathesis protocol.